通过活性阴离子聚合和原子转移自由基聚合相结合制备新型梳形聚合物

【作者】 李爱香；

【导师】 周其凤； 鲁在君；

【作者基本信息】 山东大学 ， 高分子化学与物理， 2006， 博士

【摘要】 梳形聚合物作为一类具有特殊链构造的高分子，可用作热塑性弹性体、稳定剂、分离用薄膜、水凝胶、药物载体等，也可用来制备纳米材料，因此这类聚合物的分子链构造设计越来越引起人们的关注。 结构清楚的梳形聚合物通常采用活性聚合的方法来合成。在众多的活性聚合方法中，活性阴离子聚合发展得最为成熟，是迄今进行高分子链构造设计的最佳方法，但是可聚合单体的范围有限。原子转移自由基聚合(ATRP)虽然发展较晚，但是反应条件温和，单体选择范围很宽。 本文综合上述两种聚合方法的优点，选择活性阴离子聚合与ATRP相结合制备了三种具有新型链构造的梳形聚合物：高支化梳形聚合物，梳形离聚物和蜈蚣形聚合物。主要研究内容和结果如下： 1．通过ATRP聚合4-乙烯基苄氧基二苯甲酮，合成了含二苯甲酮侧基的聚苯乙烯，然后利用Wittig反应，将二苯甲酮基团定量的转化为二苯基乙烯(DPE)基团，得到含DPE侧基的聚苯乙烯主链。利用类似方法还合成了含环氧侧基的聚苯乙烯主链。用红外光谱(IR)、核磁氢谱(~1H NMR)和凝胶渗透色谱(GPC)等测试方法对这两种含侧基官能团的主链聚合物分别进行了详细表征，证明得到了分子量可控的、窄分布的含DPE侧基和环氧侧基的聚苯乙烯。 2．利用活性聚苯乙烯阴离子(PSLi)与含DPE侧基的聚苯乙烯进行偶联反应，制备了每个重复单元含一条侧链的高支化梳形聚苯乙烯。用IR、~1H NMR、GPC和SLS(光散射)等测试方法对其进行了详细表征，并讨论了PSLi与DPE基团的比例和主链与侧链的分子量等因素对接枝率的影响，结果表明PSLi与DPE官能团的偶联反应是定量的，可以通过调节PSLi与DPE官能团的加料比来控制接枝率。 3．PSLi与含DPE侧基的聚苯乙烯主链进行偶联反应，生成的二苯基甲基阴离子可进一步与亲电试制N，N-二甲氨基-3-氯丙烷反应，得到含氨基的高支化梳形聚合物。用盐酸对其进行季铵化反应后形成含阳离子的梳形离聚物。用~1H NMR、GPC和滴定等方法对其结构和官能化产率进行了详细表征。氨基滴定的结果表明，氨基官能化产率是定量的。离聚物在水溶液中可以自组装更多还原

【Abstract】 As a kind of polymer with unique chain architectures, comb-like polymers have been used as thermoplastic elastomers, separated membrane, hydrogel, compatibilizer, and drug delivery carriers etc. In addition, they can also be used to prepare nanomaterials. Therefore, the design of chain architecture of comb-like polymers has attracted more and more interest.Well-defined comb-like polymers are usually synthesized by living polymerizations. Among all the living polymerization methods, anionic polymerization has been extensively studied, and is the best method to design chain architectures. However, anionic polymerization can only polymerize a limited range of monomers. Atom transfer radical polymerization (ATRP) has been developed late, but its reaction condition is gentle. More importantly, it can polymerize a wide range of monomers.In this thesis, we described the synthesis and characterization of three comb-like polymers with novel chain architectures by combination of living anionic polymerization and ATRP, including highly branched comb-like polymers, comb-like ionomers, and centipede-like copolymers. The brief contents and results are as follows:1. ATRP of 4-vinylbenzyloxy benzophenone followed by Wittig reaction led to polystyrene backbone with 1, 1-diphenylethene (DPE) pendent groups. In addition, the polystyrene backbone with epoxy pendant groups was also prepared by the similar method. These backbone polymers were characterized by ~1H nuclear magnetic resonance (~1H NMR) spectroscopy, Fourier-transform infrared (IR) spectroscopy, and gel permeation chromatography (GPC) respectively in detail. The results showed that backbone polymers with DPE and epoxy pendant groups, having controlled molecular weight and narrow distribution, were obtained successfully.2. The novel highly branched comb-like polystyrenes with one side chain per repeating unit were synthesized by coupling reaction of living polystyrene carbanions (PSLi) with DPE pendant groups of polystyrene backbone. The resulting polymers were characterized by ~1H NMR, IR, GPC, and SLS in detail. The effects of [PSLi] and更多还原